JPS58157756A - Cyanoacylamide compound, manufacture and hardenable mixture - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel 1N-cyanoacylamide compound, its production method and its use. 12G-functional compounds, i.e., compounds containing two different functional and reactive groups in the molecule, are suitable for applications where a B-stage resin is required.
For example, in the production of prepreg or composite materials, especially for vehicle interiors. For example, a 2'1 northern compound having a polymerizable binary bond and a glycidyl group in its molecule; No. .539 and German Openness, ME1-Publication No. 2,154,826
It is known from No. - Linear polymers obtained by polymerizing the 211 [bonds] of such monomers and containing several glycidyl groups or reactive monocyclic groups in the molecule have historically been treated with curing agents and/or It can be converted to a thermosetting state simply by adding a crosslinking agent.

Therefore, the object of the present invention is to be able to transform into a thermosetting resin without causing problems in the two-step modification reaction.
The present invention is to provide a bifunctional compound which has other useful uses, for example in the production of prepregs and composite materials.

The present inventors have discovered that a certain Yuzu N-cyanoazuramide compound containing a polymerizable Type 2 bond and a thermally crosslinkable cyanoamide group in one molecule meets these requirements.

Prompted, the present invention provides the following formula = Le 0 11 C1-j2= C-1 et al-N -C-R+ (I
)N (wherein, 1tl represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloargyl group having 5 to 8 carbon atoms, or an aryl group having 6 or 10 ring carbon atoms;
If a bird represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (~; and a bird represents an alkylene or arylene alkylene group having up to 12 carbon atoms, or a horse represents a hydrogen atom, a tow also represents The present invention relates to a hecyanoacylamidated metal compound represented by (also representing an oxyalkylene group having 12 or less carbon atoms).

The alkyl group I71 may be linear or branched, non-1w substituted or substituted, or may have an intervening ether oxygen atom. Examples of suitable fc substituents are nitrile and nitro groups. Cycloalkyl M, ltI can also be substituted by this cyanosyl group, if appropriate. As examples of alkyl groups, the following may be mentioned: methyl, cyanomethyl, ethyl,
n-propyl, isopropyl, n-butyl, sec-phthyl, n-pentyl, 2-pentyl, rhohexyl, n-heptyl, 6-heptyl, n-octyl and n-dodecyl.

The aryl group R1 can be unsubstituted or, for example, one or two
halogen atoms, especially earth or bromine atoms, 1 or 2
nitro groups, or 1 to 2 C1 to C4, especially C1 and C2, can be substituted by 2 alkyl or alkoxy groups. Examples of aryl groups in this persimmon include: phenyl, p-nitrophenyl, 3,5-dinitrophenyl, p
-tolyl, 0-tolyl, 4-chloro-1-nitrophenyl, 2-methoxyphenylnaphthyl and β-chlornaphthyl.

Most of the groups are linear unsubstituted groups, such as methylene, ethylene, oxyethylene, butylene or phenylenemethylene.

In formula (■), lt is preferably -1-J, CHfC
H, fn (in the formula, n = 0fx i6), CH3-(C
, 1-12-)7-CH-.

Member CH2-Cf-1s (C113-Cn-, (ci-t3 amount C-, NC-C
H2-.

-CH5, -C2H5, -CL, -Br, -N
02 or -0Cl-13, and Peng is 10H2
-, or square-(J-+CH2trrljp (in the formula,
m and p represent 1 to 6, p preferably represents 1 or 2.

Compounds of formula I have the following formula lI: 11 θ
Φ H,, -e -N -CN M (II) (
In the formula, 1 mole of 1N-cyanocarboxylic acid amide salt represented by "M" represents a sodium or potassium cation, and 1 tl represents tl# of -e = co□ (Ill) (
In the formula, X represents a radical, bromine or iodine atom, and 1 mole of a halogen compound represented by AjJ i4 represents one's own property in a polar neutral bath medium. The compounds represented by formulas (1) and (2) are known compounds. Examples of compounds of the formula H that may be mentioned are the potassium salts and especially sodium em of acetyl cyanamide, benzoyl cyanamide and N-cyanocyclohexylcarboxylic acid amide.

Examples of suitable compounds of formula Ill are allyl chloride, allyl bromide, methallyl chloride, β-chloroethyl vinyl ether and vinylbenzyl chloride.

Examples of suitable neutral bath media are dimenalformamide, dimethylacetamide, dimethylglobionamide, hemeterpyrrolidone, dimethylsulfoxide, sulfolane, hexamethyloxotriamide, tetramethylurea or the compound itself to be synthesized. be.

The polar, neutral bath medium used in the process for preparing compounds of formula I is not reliable. Generally, the bath medium contains 5 to 20 starting compounds.
It can be used in amounts to form a 70% strength F4 liquid, preferably a 10-50% strength bath liquid.

The process can be carried out over a wide temperature range from about 20° to 180°C. The preferred reaction temperature is 40° to 12°C.
It is 0°C.

The hecyanoacylamide compounds according to the invention have many possible uses, 1 and thus, for example, as starting materials for the production of isomelamines, as curing agents for epoxide resins, and in the H-building of thermally crosslinkable linear homopolymers and copolymers. Can be renewed.

In the production of isomelamine from the compound of the present invention,
N-alkyl cyanamides which can be piezoelectrically polymerized to form trialkylene melamines are formed by hydrolysis or alcoholysis of compounds of formula 1.

Furthermore, the N-cyanoacylamide compound of the present invention also includes:
It was discovered that the curing firmness is true to that of epoxide resin.

The invention therefore also relates to the use of the compounds of the invention in curable mixtures consisting of epoxide resins and N-cyanoacylamide compounds.

The amount of N-cyanoacylamide compound used as a curing agent in these curable mixtures is N per 1 epoxide.
-cyanocarboxylic acid amide 4 i')+11 0.7
El il, 1.25th'rIk existence-j-ruyouf
Preferably, the N-cyanoacylamide compound and the epoxide resin component are used in equivalent amounts.

The N-cyanoacylamide compounds of the present invention can be converted by themselves or together with other polymerizable monomers into linear polymers by one conventional method. Excessive monomers that can be added to the compounds of the present invention include acrylic acid-based compounds, such as esters formed from acrylic acid or methacrylic acid and alcohols or phenols (such as methyl acrylate, butyl acrylate, methyl methacrylate). , acrylonitrile, methacrylateryl and ethylene glycol dimethacrylate; and other reactive olefinically unsaturated monomers such as styrene, divinylbenzene, vinyl acetate, maleic anhydride and half-esters and diesters of maleic acid (e.g. dimethyl or dibutyl maleate). It is. Preferred monomers are hydroxyalkyl esters of (meth)acrylic acid, such as 2-hydroxyethyl acrylate, 2-
They are hydroxyethyl methacrylate and 2-hydroxypropyl (meth)acrylate.

Examples where it is preferred to use conventional free radical-forming catalysts in the polymerization or copolymerization include hydrazine compounds such as hydrazine hydrochloride, organometallic adducts such as tetoethyl lead, and Also, especially α, α
- aliphatic azo compounds and organic peroxides or persalts, such as azoisobutyrodinitrile, such as peracetic acid, acetyl peroxide, chloroacetyl peroxide, benzoyl peroxide,
Chlorobenzoyl peroxide, benzoylacetyl peroxide and 6-butyl hydroperoxide, and also inorganic peroxides such as peroxides, alkali metal percarbonates, alkali metal persulfates or alkali metal perborates. , and also hydrogen peroxide, which can replace the more expensive benzoyl peroxide. The addition rate is adjusted by known methods depending on the desired reaction progress or the desired properties of the polymer. It is advantageous to use about 0.05 to 10% by weight of catalyst based on the total amount of monomer mixture, and either the entire amount of catalyst is added at the beginning of the polymerization or only a portion is added during the polymerization process. Add in portions.

In some cases, especially in the case of homopolymerization, ionic catalysts should be used, such as Lewis acids. With regard to temperature and medium (absence of solvents or baths), customary polymerization conditions can be used for the polymerization or copolymerization.

The N-cyanoacylamide compounds of the invention or their mixtures with other polymerizable monomers can be used in the protection of Table 1n1 as impregnating and casting resins and in particular in the production of H-1 porridge and composite materials. It can be used for one history.

The N-cyanoacylamide compound of the present invention or its mixture with other polymerizable monomers or epoxide resins may be added at any stage prior to crosslinking or curing to include extenders, fillers and reinforcing agents, pigments, dyes, organic solvents, etc. Customary modifiers such as plasticizers, rheological modifiers, thixotropic agents, flame retarding substances and mold release agents can also be added.

Although these examples illustrate the invention in more detail, the invention is not limited to these examples.

Example 1: Sodium acetyl cyanamide in N-cyano-β-methallylacetamide dimethylformade ζ” 4 ss, or (o, s mol)
and β-methallyl chloride 49.11 (0.5 mol +
10% excess) for 2 hours and 25 minutes at 124° to 130° C. in a glass apparatus equipped with a stirrer, thermometer, reflux condenser and drying tube.33 The reaction mixture is then filtered with suction, The mixture is concentrated on a rotary evaporator at 70° C. in a vacuum chamber, and the residue is purified by fractional distillation. This gives 468 volts (67.7 factor of theory) of a colorless, transparent liquid with a boiling point of 87 x/234 mbar.

C60,85% C6[J,66% 1-1 7.30% 1-4 7.414yIN 2
The 0.28% I'420.05 H-NM spectral data are consistent with the N8 contamination formula: Real mfl: N-cyano N-vinylbenzylacetamide acetyl cyanamide sodium 4233y (02 moles + 10 % excess) and vinylbenzyl chloride (approximately 4o
50.5 f (0.2 mol) of a technical mixture of isomers containing % rose component and 60% meta component were reacted for 8 hours at 48° to 50° C. in dimethylformamide. When the reaction is complete, the mixture is filtered with suction, and the solution F is stirred vigorously and then poured with ice at 500 °C. and water 50
0 ml and then the mixture is extracted with ethyl acetate. The ethyl acetate solution is dried over anhydrous sodium sulfate and subjected to 1 vacuum of 11F, the F solution is decolorized with activated carbon, the solution is P filtered and the P solution is concentrated on a rotary evaporator under reduced pressure at 40C. 0 residuals at 40°C until constant pre-1
Dry at 0.15 mbar.

A brownish viscous liquid 34.91 (Jl!l
! 871% of m 116°) is raw IJZ L, this is tl
-bulbtube distillati
on) at 160° to 145° C. and 10.7 mbar.

Elemental analysis Piece V calculated value Actual value C71.98% C71.83% )1 6.04% 8 6.51
%N15.99% N15.87% H-NM)? The spectral data are consistent with the structural formula below: Example 6: N-cyano-N-allylacetamidoacetyl cyanamide sodium 1n 159.19 (15 mol) and allyl chloride 157.8f (1,5 mol + 2
0% PerII) f-sulfolane 400ml. Inside, 7
0" to 127 to 7 (9 hours and 45 minutes), react as in Example 1 and process mixture M as in Example 1. Colorless, Arm, temperature 8°C/45 mbar, 121
7f (654% of 111L) is obtained.

Elemental analysis: Calculated value Actual value 058.06% C58.09% 8 6.50% I-J 6.57 ChiN 22.5
7%N 22.56%H-NMR spectrum data is consistent with the structural formula below, 1"6.

1 Example 4: Sodium 4-106.1r(1
, 0 mol), 2-chloroethyl vinyl ether 117.
1 (1,1 mol) and potassium iodide 8.5 r (5
0 mE) in 400 d of dimethylformamide, 7
React at 6-127°C for 1 hour and 5 minutes according to Example 2,
- and the mixture is treated as in Example 1. By fractionating the crude product, it becomes clear, colorless +7),
f! Point IIi, 128°C, 29 mbar, is 69,
Of (447% of jlj i's 1st shift) I'm kidnapped.

Elemental analysis second w1 limit value Actual value C54,54% C54,45 ChiB 6.54% H665% N1B, 17% N 17.92%In-
The NMR spectrum is consistent with the following structure: According to Example 1 below, in Example 1-Vl.
C*'! In addition, fc N-cyano-,N-vinylbenzylacetamide is used as a monomer for the production of polymers and as a softening agent for epoxides.

The reactivity of N-cyano-N-vinylbenzylacetamide weighed by itself and with catalysts or epoxide trees is determined on the basis of the gelation time and on the basis of the thermal fraction. Glass transition Temperature and tensile shear
Strength is used to express the percentage of crosslinked polymer.

Kelization times are measured at individual temperatures. This is a hot brake in which a small amount of the substance to be tested is adjusted to the desired temperature.
This is done by measuring the gelation time of the sample by placing it in the center of the plate (also known as a plate) to determine the time required to reach the 3-19th floor.

To determine reactivity by differential thermal analysis (DTA),
Approximately 20 mg of the substance to be tested is weighed out into an aluminum crucible particularly suitable for this purpose. This crucible was sold to Mettler-Instrument.
AG), Greifensee, Switzerland ((J-Grei
fensee), 'f'A of g@
2 0 0 0 1) 'L'A 4 in the measurement room of the device
It is heated at a heating rate of 1° C./min and the temperature difference compared to a simultaneously heated empty crucible is continuously recorded. Reaction initiation temperature (1” s), maximum reaction rate temperature (TfLRma
x, ) and the reaction end point temperature (Tg) are read from the curve thus obtained.The enthalpy of reaction is calculated from the area between the curve obtained and the baseline.

The glass transition temperature is measured by placing each of the materials to be tested 42 into a thin-walled aluminum crucible approximately 5 crn in diameter and curing the sample therein. A sample of the crosslinked polymer is thus taken from the disk and the glass transition point of this sample is determined by differential thermal analysis (J'I'A). The specific heat changes at the transition point;
It is recorded as the transition point within the curve recorded by a TA-2000DTA instrument manufactured by Greifensee, Inc.

The glass transition temperature (GTT) makes it useful to draw conclusions regarding the thermal deformation point of the polymer obtained.

The tensile shear strength was determined by preparing a small amount of the material to be eaten by aIA1, which had been previously ground to roughness and degreased by washing with a bath medium.
Anticoroda with dimensions of 70X25X2.5mm
Measure by applying it to the edge of a test piece made of B. Two of these test pieces are adjusted with a gauge so that the edge on which the substance to be tested is applied is only 12 fins clear in the troughs. Define with thin metal until hardened according to its properties. Next, for gluing, the tensile shear strength of the joint is determined, ])IN 53,28
With the bends specified in 3 (1,) I N = German Industrial Standard), three 1llll about the angle
Mf is calculated by taking the average of the ffi values.

Old Shio IJ I N-cyano-N-vinylbenzylacetamide (CV
B A ) can be converted to a polymerized state using only heat without adding a catalyst. In this process, CV B A
was found to be reactive even in the absence of catalytic additives. A molding material having a tensile shear strength t7N/= 01188°C is prepared after curing at 120°C. , When further cured at 180°C, ()i
'T increases by only 5℃, but the tensile shear strength increases by 50℃.
% increase.

The reactivity of CVI3A and the 1! E Write the negative number on Table 1.

According to the thermal properties of both fi and the gelation time direction, if one addition of 6th bunalperoxybiparate 1131'I to CVI3AI000, the reaction time is 1 year. Yes () TT84℃ and tensile shear strength 4.4N1mA
has. When cured at 180℃ (+TT only increases by 6℃, the tensile shear strength is about 65%)
(see data in Table 1)
00 copies. As shown in Table 1, 120℃
The molding material obtained after curing at GT Ta7℃
and has a tensile shear ll7T strength of 5.4 N/ff. 1
When heated to 80℃ (J 'L' T is 8C
and the tensile shear strength increases by 50 lbs.

Epoxide A1 month conversion: CV BA with epoxide, 21 stitches/hour, 85,000mpa at softening temperature 50℃ and viscosity 100℃
In solid unmodified bisphenol A diglycidyl ether (epoxide resin ■) of s, the thornization catalyst and promoter were dissolved in CVIJA, the product was mixed roughly by hand with the simulated powdered epoxide resin 1, and The mixture is then incorporated by milling on a three roll mill.

Application Example ■ CVIJA and Evogicide resin ■ are mixed in a ratio of 1 mole per 1 epoxide equivalent as described above. 14
After curing at 0°C, a molding material with a tensile shear strength of 22.1 N/ylj is obtained. After curing at 180°C, a GTT of 7 As the temperature increased, the tensile shear strength increased by more than 30% to 29.5
Become N/J.

Application Example ■ As an accelerator, 0.005 mol of 1-methylimidazole/approx. of epoxide is added to the curable epoxide resin mixture used in Application Example IV cf12. The molding material obtained after curing at 140°C has (i'll'T85°C and a tensile shear strength of 13.4 N/J. After further curing at 180°C, (J 'f T increases by 8° C. and tensile shear strength increases by about 50%.

Application Example 1: Both 6-butylberoxypiparate and 4% by weight Co octoate in styrene as accelerators are added to the curable 4η baby fat mixture used in Application Example 2. Thermal analysis shows two exothermic reactions during the curing process. 1
His molding material cured at 20°C (1'T 77°C and has a tensile shear strength of 15.2 N/mj. 180°C
Upon further curing at
.

Usage example■ H2O10m/! K (monthly 43.1' (0,060)
7 mol) is added to N-cyano-N-allylacetamide y, 44y (o, o 6 mol). After adding ethanol 6-, the mixture becomes homogeneous and an exothermic reaction occurs. After a short time an oil separates out; this can be dissolved by adding ethanol 3 and boiling the mixture briefly.

After cooling, the mixture is diluted with 10 ml of H2O and extraction is carried out with 3 portions of chloroform (20, 10 and 10-). When the extract is condensed on a rotary evaporator, 4.77 f of a colorless oil is produced, which is purified by distillation in an open spherical tube to yield 5.549 f of 1.3.5-dolylylisomelamine (theoretical value). 71.9%), which is 0.026'! It boils at 105 DEG-115 DEG C. at J bar, solidifies to a crystalline state at room temperature, and is more than 97% tough according to gas chromatography.

Min @: C1□l-1,8N6 (IW -246,52)
: Calculated value: C5B, 52% Actual value: C58,
52%1-1 767% H71
4% N34.12% N34.57
% Usage Example ■ 16 parts (05% by weight) of dibenzoyl peroxide are added to a mixture consisting of 154 parts (1 mol) of N-cyano-N-2-vinyloxyethylacetamide and 198 parts (1 mol) of maleic anhydride. A clear solution with very low viscosity is obtained after a few minutes. Good reactivity is observed as determined by gelation time and thermal analysis. The molding material obtained after curing at 120°C for 6 hours has a glass transition temperature of 95°C.
The temperature can be increased by 65°C by curing for 6 hours at 180°C.

Claims (6)

[Claims] (1) The following formula ■: N (wherein, 1 mol represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, or an alioid having 6 or 10 carbon atoms in the ring) - clothed with a group;
The bird carries a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; therefore, one carries an alkylene or arylene alkylene group having up to 12 carbon atoms, or the bird carries a hydrogen atom. , 1 also represents an oxyalkylene group having 12 or less carbon atoms). (2) In formula I, 1 is -1-L c1f3goC
H□i (n is 0 to 6), CHiCH21-
CH-. CH2-CH3 ((川sj”r C1-1-r (eHajr
Cr Ne-CH2-+=I-J, -CI43
．． -C2H6, -CL, -Br, -1'JO2 or -UCH3), and 1 (3 is -
CH2-, or +U + CH2- (in the formula, m and p each represent 1 to 76) or a compound vlJ as described in section 1. (3) The compound according to claim 1, which is N-cyano-N-vinylbenzylacetamide, N-cyanohemethallylacetamide and N-cyanoheallylacetamide. (4) Formula II: (wherein, M represents a sodium or potassium cation, and 1tl is a hydrogen atom, having 1 to 20 carbon atoms.
(representing an alkyl group having 5 to 8 carbon atoms or an aryl group having 6 or 10 carbon atoms in the ring) 1 mole of an N-cyanocarboxylic acid amide salt represented by the following formula (2): 几2 - X -C==Cn2(III) (wherein, When it represents an alkylene or arylene alkylene group having up to 12 carbon atoms, or when It2 represents a hydrogen atom, the island is a sweet group having up to 12 carbon atoms,
1 mole of a halogen compound represented by the following formula: A method for producing an N-cyanoacylamide compound represented by (5) The following formula I: l-〇11 CI-1□ -c -1(, -N -C-1 is also 1
(1) N (in the formula, l (・l is a hydrogen atom, the number of carbon atoms is 1 to 2
0 represents an alkyl group, a cycloalkyl group having 5 to 8 carbon atoms, or an aryl group having 6 or 10 ring atoms; l (2 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; and R3 represents an alkylene or arylene alkylene group having up to 12 carbon atoms, or when f represents a hydrogen atom, (ii) also represents an oxyalkylene group having up to 12 carbon atoms); N-cyanoacylamide compound represented and 11 in one molecule
A curable mixture comprising an epoxide resin having more than 1t'd of epoxide content. (6) A curable mixture according to claim 5 for producing a linear homopolymer or copolymer.